Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same

ABSTRACT

This invention relates to a composition useful as an oral care composition comprising an organophosphate material, additional oral care composition ingredients, for example, a surfactant agent, and optionally an abrasive agent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Continuation of U.S. patent application Ser. No. 12/137,647filed Jun. 12, 2008 which claims the benefit of U.S. Provisional PatentApplication No. 60/943,490 filed Jun. 12, 2007, both of which areincorporated by reference in their entirety.

FIELD OF THE INVENTION

This application relates to compositions useful in dentifrices and otheroral care products. Particularly the invention relates to oral carecompositions containing a surfactant agent consisting essentially ofwater soluble salts of monoalkyl and dialkyl phosphate esters. Theinvention includes oral care formulations including mono-, di-, andpolyol phosphate esters as surface modification agents to changeadhesion properties of these surfaces for hydrophobic as well ashydrophilic materials.

BACKGROUND OF THE INVENTION

The various benefits of using a variety of phosphate esters, as theirsalts, in oral care formulations have been reported for decades. U.S.Pat. No. 4,152,421 refers to the use of alkali metal or alkanolaminesalts of alkyl phosphate esters in dentifrice formulations. It cites thehigh foaming property of the high monoalkyl content phosphate esters(monoalkyl:dialkyl phosphate, or MAP:DAP, weight ratio of 70:30-100:0)as novel, in combination with the “known” property of having nosubstantial after effects on the tastes and flavors of foods and drinks,especially citrus juices. The concept and range of structures isexpanded in a subsequent U.S. Pat. No. 5,370,865, which emphasizes thepleasant taste of basic amino acid salts, specifically with lysine,arginine and histidine. Another early patent, U.S. Pat. No. 4,264,580,covers the incorporation of 0.2-1.0% of an anionic phosphate estermixture (monoalkyl:dialkyl weight ratios of 1:10 to 10:1) to reduce thegrain formation in a sodium lauryl sulfate-calcium carbonate compositionto produce a smooth paste. U.S. Pat. No. 4,350,680 asserts reduction inthe sloughing or desquamation of oral mucosa during tooth brushingaction if at least 0.2% of an anionic phosphate ester surface activeagent is used as an additional surfactant to sodium lauryl sulfate. U.S.Pat. No. 5,019,373 asserts special advantages for the incorporation ofshorter alkyl chain (C6 to C9) dialkyl phosphate esters, particularlydioctyl phosphate. The phosphate ester concentration at 2-4 wt. % in thedentifrice formulation. Evidence for anti-caries activity was offered,which showed a lower rate of calcium demineralization on teeth (invitro) treated with 1% dioctyl phosphate solution compared to both a 1%sodium lauryl sulfate, which was similar to plain water (placebo), and 1ppm sodium fluoride (the positive control).

SUMMARY OF THE INVENTION

The present inventions uses mono-, di-, and polyol phosphate esters(like PEG phosphate esters, PPG phosphate esters, glycerine phosphateesters) to provide multiple benefits to oral care formulations. Theconcentrations in which they may be used can vary depending on theintended purpose and the amount of benefit desired. These molecules witha hydrophilic nature are expected to assist in removing stains fromteeth. They may also assist in preventing staining of teeth by beingadsorbed onto teeth. The oral hygiene compositions of the inventioninclude: providing an ablatable coating for anti-adherence of stain andbacteria to teeth; desensitization of teeth having dentinalhypersensitivity; low irritancy and improved tissue compatibility ortolerance; increased deposition of various ingredients, includinganti-microbials, flavor oils; compatibility with peroxide whiteningagents; and anti-tartar characteristics.

In a first aspect, the present invention is directed to an oral carecomposition, comprising:

(a) from about 10% to about 99% of at least one ingredient selected fromthe group consisting of a polishing agent (abrasive agent), sudsingagents (surfactants), a binder, a humectant, a medicinal agent, peroxidesources, alkali metal bicarbonate salts, thickening materials, water,titanium dioxide, flavor agents, sweetening agents, xylitol, coloringagents, water and mixtures thereof, and(b) an ionic hydrophyllizing agent comprising:(b)(I) an organophosphorus material selected from:

-   -   (b)(I)(1) organophosphorus compounds according to structure (I):

-   -   wherein:        -   each R¹ is and each R² is independently absent or O,            provided that at least one of R¹ and R² is O,        -   each R³ is independently alkyleneoxy, poly(alkyleneoxy),            which may optionally, be substituted on one or more carbon            atom of such alkyleneoxy, or poly(alkyleneoxy) group by            hydroxyl, alkyl, hydroxyalkyl, alkoxy, alkenyl, aryl, or            aryloxy,        -   R⁵ is and each R⁴ is independently absent or alkyleneoxy,            poly(alkyleneoxy), which may optionally, be substituted on            one or more carbon atom of such alkyleneoxy, or            poly(alkyleneoxy) group by hydroxyl, alkyl, hydroxyalkyl,            alkoxy, alkenyl, aryl, or aryloxy,        -   R⁶ and R⁸ are each and each R⁷ is independently H, or            (C₁-C₃₀)hydrocarbon, which hydrocarbon may optionally be            substituted on one or more carbon atoms by hydroxyl,            fluorine, alkyl, alkenyl or aryl and/or interrupted at one            or more sites by an O, N, or S heteroatom, or —POR⁹R¹⁰,        -   R⁹ and R¹⁰ are each independently hydroxyl, alkoxy, aryloxy,            or (C₁-C₃₀)hydrocarbon, which hydrocarbon may optionally be            substituted on one or more carbon atoms by hydroxyl,            fluorine, alkyl, alkenyl or aryl and/or interrupted at one            or more sites by an O, N, or S heteroatom, and        -   m is an integer of from 1 to 5,    -   (b)(I)(2) salts of organophosphorus compounds according to        structure (I),    -   (b)(I)(3) condensation reaction products of two or more        molecules of one or more organophosphorus compounds according to        structure (I), and    -   (b)(I)(4) mixtures comprising two or more of the compounds,        salts, and/or reaction products of (b)(I)(1), (b)(I)(2), and        (b)(I)(3),        (b)(II) a vinyl alcohol material selected from:    -   (b)(II)(1) polymers comprising monomeric units according to        structure (I-a):

-   -   (b)(II)(2) salts of polymers (b)(II)(1),    -   (b)(II)(3) reaction products of two or more molecules of one or        more polymers (b)(II)(1), and    -   (b)(II)(4) mixtures comprising two or more of the polymers,        salts, and/or reaction products of (b)(II)(1), (b)(II)(2), and        (b)(II)(3).

The invention further relates to the use of organophosphorus material ina dentifrice, particularly standard toothpaste.

The invention also relates to a tooth cleaning product comprising anorganophosphorus material, an abrasive agent (polishing agent) andoptionally a liquid.

The invention provides a mouthwash comprising:

-   -   (a) anti-staining agent comprising the organophosphorus material        described herein;    -   (b) alcohol; and    -   (c) water.

Additionally, the longer term use of the organophosphorus material baseddentifrice in accordance with the invention has an unexpectedly longlasting, beneficial therapeutic effect.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a photograph of egg-shell brushed with commercialtoothpaste, then stained with green (left) and black (right) tea, andthen brushed again with commercial tooth-paste.

FIG. 2 shows a photograph of egg-shell brushed with commercialtoothpaste plus 20% PEG400 phosphate ester (polyethylene glycol 400phosphate ester), then stained with green (left) and black (right) tea,and then brushed again with tooth-paste plus 20% PEG400 phosphate ester.

FIG. 3 shows a photograph of egg-shell brushed with commercialtoothpaste plus 20% SDS, then stained with green (left) and black(right) tea, and then brushed with commercial toothpaste plus 20% SDS.

FIG. 4 shows a photograph of egg-shell brushed with commercialtoothpaste plus 20% PEG1000 phosphate ester, then stained with green(left) and black (right) tea, and then brushed again with commercialtoothpaste plus 20% P1000 phosphate ester.

FIG. 5 shows a droplet of hexadecane under pure deionized water on CaCO₃crystal.

FIG. 6 shows a droplet of hexadecane under 1 wt. % PEG 1000 phosphateester on CaCO₃ crystal pretreated with PEG1000 phosphate ester to showthe adsorption of PEG1000 phosphate ester onto the CaCO₃ crystalincreases the contact angle of hexadecane on CaCO₃ under water.

FIG. 7 is FIG. 5 labeled to show the contact angle.

FIG. 8 is FIG. 6 labeled to show the contact angle.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the terminology “hydrophobic surface” means a surfacethat exhibits a tendency to repel water and to thus resist being wettedby water, as evidenced by a water contact angle of greater than or equalto 700, more typically greater than or equal to 90°, and/or a surfacefree energy of less than or equal to about 40 dynes/cm.

As used herein, the terminology “hydrophilic surface” means a surfacethat exhibits an affinity for water and to thus be wettable by water, asevidenced by a water contact angle of less than 70°, more typically lessthan 60° and/or a surface energy of greater than about 40 dynes/cm, moretypically greater than or equal to about 50 dynes/cm.

As used herein in reference to a hydrophobic surface, the term“hydrophilizing” means rendering such surface more hydrophilic and thusless hydrophobic, as indicated by a decreased water contact angle. Oneindication of increased hydrophilicity of a treated hydrophobic surfaceis a decreased water contact angle with a treated surface compared tothe water contact angle with an untreated surface.

A used herein in reference to a substrate, the terminology “watercontact angle” means the contact angle exhibited by a droplet of wateron the surface as measured by a conventional image analysis method, thatis, by disposing a droplet of water on the surface, typically asubstantially flat surface, at 25° C., photographing the droplet, andmeasuring the contact angle shown in the photographic image.

Surface energy is estimated using the Young equation:cos(θ)*γ_(lv)=γ_(sv)−γ_(sl)with the contact angle α, the interfacial energy y_(sv) between thesolid and the vapor phase, the interfacial energy γ_(sl) between thesolid and the liquid phase, and the interfacial energy γ_(lv) betweenthe liquid and the vapor phase, and γ_(sv) represents the surface energyof the solid.

As used herein, “molecular weight” in reference to a polymer or anyportion thereof, means to the weight-average molecular weight (“M_(w)”)of said polymer or portion, wherein M_(w) of a polymer is a valuemeasured by gel permeation chromatography and M_(w) of a portion of apolymer is a value calculated according to known techniques from theamounts of monomers, polymers, initiators and/or transfer agents used tomake the said portion.

As used herein, the notation “(C_(n)-C_(m))” in reference to an organicgroup or compound, wherein n and m are integers, means that the group orcompound contains from n to m carbon atoms per such group or compound.

The oral formulation of the present invention may be in the form of atoothpaste or dentifrice. The term “dentifrice”, as used herein, meanspaste, gel, or liquid formulations unless otherwise specified. Thedentifrice composition may be in any desired form, such as deep striped,surface striped, multilayered, having the gel surrounding the paste, orany combination thereof. Each dentifrice composition will be containedin a physically separated compartment of a dispenser and dispensedside-by-side.

The term “oral formulation” as used herein means the total dentifricedelivered to the oral surfaces. The oral formulation is a combination ofthe two or more dentifrice compositions. The oral formulation is aproduct, which in the ordinary course of usage, is not intentionallyswallowed for purposes of systemic administration of particulartherapeutic agents, but is rather retained in the oral cavity for a timesufficient to contact substantially all of the dental surfaces and/ororal tissues for purposes of oral activity.

The term “aqueous carrier” as used herein means any safe and effectivematerials for use in the oral compositions of the present invention.Such materials include abrasive polishing materials, peroxide sources,alkali metal bicarbonate salts, thickening materials, humectants, water,surfactants, titanium dioxide, flavor system, sweetening agents,xylitol, coloring agents, and mixtures thereof.

The present compositions comprise essential components, as well asoptional components. The essential and optional components of thecompositions of the present invention are described in the followingparagraphs.

Compositions for oral care include a wide variety of products, such astoothpastes, mouthwashes, and rinses.

Organophosphorus Material

The present invention includes oral care compositions comprising asurface active agent and a hydrophilizing agent comprisingorganophosphorus material selected from:

-   -   (1) organophosphorus compounds according to structure (I):

-   -   wherein:        -   each R¹ is and each R² is independently absent or O,            provided that at least one of R¹ and R² is O,        -   each R³ is independently alkyleneoxy, poly(alkyleneoxy),            which may optionally, be substituted on one or more carbon            atom of such alkyleneoxy, or poly(alkyleneoxy) group by            hydroxyl, alkyl, hydroxyalkyl, alkoxy, alkenyl, aryl, or            aryloxy,        -   R⁵ is and each R⁴ is independently absent or alkyleneoxy,            poly(alkyleneoxy), which may optionally, be substituted on            one or more carbon atom of such alkyleneoxy, or            poly(alkyleneoxy) group by hydroxyl, alkyl, hydroxyalkyl,            alkoxy, alkenyl, aryl, or aryloxy,        -   R⁶ and R⁸ are each and each R⁷ is independently H, or            (C₁-C₃₀)hydrocarbon, which hydrocarbon may optionally be            substituted on one or more carbon atoms by hydroxyl,            fluorine, alkyl, alkenyl or aryl and/or interrupted at one            or more sites by an O, N, or S heteroatom, or —POR⁹R¹⁰,        -   R⁹ and R¹⁰ are each independently hydroxyl, alkoxy, aryloxy,            or (C₁-C₃₀)hydrocarbon, which hydrocarbon may optionally be            substituted on one or more carbon atoms by hydroxyl,            fluorine, alkyl, alkenyl or aryl and/or interrupted at one            or more sites by an O, N, or S heteroatom, and        -   m is an integer of from 1 to 5,    -   (2) salts of organophosphorus compounds according to structure        (I),    -   (3) condensation reaction products of two or more molecules of        one or more organophosphorus compounds according to structure        (I), and    -   (4) mixtures comprising two or more of the compounds, salts,        and/or reaction products of (1), (2), and (3).

Suitable organophosphorus materials are also described in U.S.provisional patent application Nos. 60/842,265, filed Sep. 5, 2006 and60/812,819, filed Jun. 12, 2006, both incorporated herein by reference.

As used herein, the term “alkyl” means a monovalent saturated straightchain or branched hydrocarbon radical, typically a monovalent saturated(C₁-C₃₀)hydrocarbon radical, such as for example, methyl, ethyl,n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, or n-hexyl,which may optionally be substituted on one or more of the carbon atomsof the radical. In one embodiment, an alkyl radical is substituted onone or more carbon atoms of the radical with alkoxy, amino, halo,carboxy, or phosphono, such as, for example, hydroxymethyl hydroxyethyl,methoxymethyl, ethoxymethyl, isopropoxyethyl, aminomethyl, chloromethylor trichloromethyl, carboxyethyl, or phosphonomethyl.

As used herein, the term “hydroxyalkyl” means an alkyl radicalsubstituted on one of its carbon atoms with a hydroxyl group.

As used herein, the term “alkoxyl” means an oxy radical substituted withan alkyl group, such as for example, methoxyl, ethoxyl, propoxyl,isopropoxyl, or butoxyl, which may optionally be further substituted onone or more of the carbon atoms of the radical.

As used herein, the term “cycloalkyl” means a saturated cyclichydrocarbon radical, typically a (C₃-C₈) saturated cyclic hydrocarbonradical, such as, for example, cyclohexyl or cyclooctyl, which mayoptionally be substituted on one or more of the carbon atoms of theradical.

As used herein, the term “alkenyl” means an unsaturated straight chain,branched chain, or cyclic hydrocarbon radical that contains one or morecarbon-carbon double bonds, such as, for example, ethenyl, 1-propenyl,or 2-propenyl, which may optionally be substituted on one or more of thecarbon atoms of the radical.

As used herein, the term “aryl” means a monovalent unsaturatedhydrocarbon radical containing one or more six-membered carbon rings inwhich the unsaturation may be represented by three conjugated doublebonds, such as for example, phenyl, naphthyl, anthryl, phenanthryl, orbiphenyl, which may optionally be substituted one or more of carbons ofthe ring. In one embodiment, an aryl radical is substituted on one ormore carbon atoms of the radical with hydroxyl, alkenyl, halo,haloalkyl, or amino, such as, for example, methylphenyl, dimethylphenyl,hydroxyphenyl, chlorophenyl, trichloromethylphenyl, or aminophenyl.

As used herein, the term “aryloxy” means an oxy radical that issubstituted with an aryl group, such as for example, phenyloxy,methylphenyl oxy, isopropylmethylphenyloxy.

As used herein, the indication that a radical may be “optionallysubstituted” or “optionally further substituted” means, in general,unless further limited, either explicitly or by the context of suchreference, that such radical may be substituted with one or moreinorganic or organic substituent groups, such as, for example, alkyl,alkenyl, aryl, aralkyl, alkaryl, a hetero atom, or heterocyclyl, or withone or more functional groups that are capable of coordinating to metalions, such as hydroxyl, carbonyl, carboxyl, amino, imino, amido,phosphonic acid, or sulphonic acid, or inorganic and organic estersthereof, such as, for example, sulphate or phosphate, or salts thereof.

As used herein, the terminology “(C_(x)-C_(y))” in reference to anorganic group, wherein x and y are each integers, indicates the groupmay contain from x carbon atoms to y carbon atoms per group.

In one embodiment, R⁶ and R³ are each and each R⁷ is independently H,(C₁-C₃₀)alkyl, (C₁-C₃₀)alkenyl, or (C₇-C₃₀)alkaryl.

In one embodiment, each R¹ and each R² is O, and the organophosphoruscompound is selected from:

-   -   (II)(1) an organophosphate ester according to structure (II):

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, and m are each as described above,

-   -   (II)(2) salts of organophosphorus compounds according to        structure (II),    -   (II)(3) condensation reaction products of two or more molecules        of one or more organophosphorus compounds according to structure        (II), and    -   (II)(4) mixtures comprising two or more of the compounds, salts,        and/or reaction products of (II)(1), (II)(2), and (II)(3).

In one embodiment, each R¹ is absent, each R² is O, and theorganophosphorus compound is selected from:

-   -   (III)(1) an organophosphonate ester according to structure        (III):

-   -   wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, and m are each as described        above,    -   (III)(2) salts of organophosphorus compounds according to        structure (III),    -   (III)(3) condensation reaction products of two or more molecules        of one or more organophosphorus compounds according to structure        (III), and    -   (III)(4) mixtures comprising two or more of the compounds,        salts, and/or reaction products of (III)(1), (III)(2), and        (III)(3).

In one embodiment, each R¹ is O, each R² is absent, and theorganophosphorus compound is selected from:

-   -   (IV)(1) an organophosphonate ester according to structure (IV):

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, and m are each as described above,

-   -   (IV)(2) salts of organophosphorus compounds according to        structure (IV),    -   (IV)(3) condensation reaction products of two or more molecules        of one or more organophosphorus compounds according to structure        (IV), and    -   (IV)(4) mixtures comprising two or more of the compounds, salts,        and/or reaction products of (IV)(1), (IV)(2), and (IV)(3).

In one embodiment, each R³ is a divalent radical according to structure(V), (VI), (VII), or (VIII):

-   -   wherein:        -   each R¹² and each R¹³ is independently H, hydroxyl, alkyl,            hydroxyalkyl, alkoxy, alkenyl, aryl, aryloxy, or two R¹²            groups that are attached to the adjacent carbon atoms may be            fused to form, together with the carbon atoms to which they            are attached, a (C₆-C₈)hydrocarbon ring,        -   R²⁰ is H, hydroxyl, alkyl, hydroxyalkyl, alkoxy, alkenyl,            aryl, or aryloxy        -   R²² is hydroxyl or hydroxyalkyl, provided that R²⁰ and R²²            are not each hydroxyl,        -   R²³ and R²¹ are each independently methylene or            poly(methylene),        -   p, p′, p″, q, and x are each independently integers of from            2 to 5,        -   each r, s, r′, r″, and y is independently a number of from 0            to 25,        -   provided that at least one of r and s is not 0,        -   u is an integer of from 2 to 10,        -   v and w are each numbers of from 1 to 25, and        -   t, t′, and t″ are each numbers of from 1 to 25,    -   provided that the product of the quantity (r+s) multiplied times        t is less than or equal to about 100, the product of the        quantity (v+r′) multiplied times t′ is less than or equal to        about 100, and the product of the quantity (w+r″) multiplied        time t″ is less than or equal to about 100.

In one embodiment, each R⁴ and each R⁵ is independently absent or adivalent radical according to structure (V), (VI), or (VII), whereinR¹², R¹³, R²⁰, R²¹, R²², R²³, p, p′, p″, q, r, r′, r″, s, t, t″, t, u,v, w, x, and y are as described above.

In one embodiment, each R³ is independently a divalent radical accordingto structure (V), (VI), or (VII) wherein R¹², R¹³, R²⁰, R²¹, R²², R²³,p, p′, p″, q, r, r′, r″, s, t, t″, t, u, v, w, x, and y are as describedabove, and R⁴ and R⁵ are each independently absent or R³.

In one embodiment, each R³ is independently a divalent radical accordingto structure (V), wherein p is 2, 3, or 4, r is an integer from 1 to 25,s is 0, t is an integer of from 1 to 2, and R⁴ and R⁵ are eachindependently absent or R³.

In one embodiment, each R³ is independently a divalent radical accordingto structure (VI), wherein the R¹² groups are fused to form, includingthe carbon atoms to which they are attached, a (C₆-C₈) hydrocarbon ring,each R¹³ is H, p′ is 2 or 3, u is 2, v is an integer of from 1 to 3, r′is an integer from 1 to 25, t′ is an integer of from 1 to 25, theproduct of the quantity (v+r′) multiplied times t″ is less than or equalto about 100, more typically less than or equal to about 50, and R⁴ andR⁵ are each independently absent or R³.

In one embodiment, each R³ is independently a divalent radical accordingto structure (VII), wherein R²⁰ is hydroxyl or hydroxyalkyl, R²² is H,alkyl, hydroxyl, or hydroxyalkyl, provided that R²⁰ and R²² are not eachhydroxyl, R²¹ and R²³ are each independently methylene, di(methylene),or tri(methylene), w is 1 or 2, p″ is 2 or 3, r″ is an integer of from 1to 25, t″ is an integer of from 1 to 25, the product of the quantity(w+r″) multiplied times t″ is less than or equal to about 100, moretypically less than or equal to about 50, and R⁴ and R⁵ are eachindependently absent or R³.

In one embodiment of the organophosphorus compound according tostructure (II):

R⁶ and R³ are each and each R⁷ is independently H or(C₁-C₃₀)hydrocarbon, which hydrocarbon may optionally be substituted onone or more carbon atoms by hydroxyl, fluorine, alkyl, alkenyl or aryland/or interrupted at one or more sites by an O, N, or S heteroatom, or—POR⁹R¹⁰, more typically, R⁶, R⁸, and each R⁷ are each H,

R⁴ and R⁵ are each absent,

each R³ is independently a divalent radical according to structure (V),(VI), or (VII), and

m is an integer of from 1 to 5.

In one embodiment of the organophosphorus compound according tostructure (II):

-   -   R⁶, R⁸, and each R⁷ are each H    -   R⁴ and R⁵ are each absent,    -   each R³ is independently a divalent radical according to        structure (V),    -   each p is independently 2, 3, or 4, more typically 2 or 3,    -   each r is independently a number of from 1 to about 100, more        typically from 2 to about 50,    -   each s is 0,    -   each t is 1, and    -   m is an integer of from 1 to 5.

In one embodiment, the organophosphorus material is selected from:

-   -   (X)(1) organophosphorus compounds according to structure (IX):

-   -   wherein:        -   p is 2, 3, or 4, more typically 2 or 3,        -   r is a number of from 4 to about 50,    -   (IX)(2) salts organophosphorus compounds according to structure        (IX), and    -   (IX)(3) mixtures comprising two or more of the compounds and/or        salts of (IX)(1) and (IX)(2).

In one embodiment of the organophosphorus compound according tostructure (II):

R⁶, R⁸, and each R⁷ are each H

R⁴ and R⁵ are each absent,

each R³ is independently a divalent radical according to structure (VI),

the R¹² groups are fused to form, including the carbon atoms to whichthey are attached, a (C₆-C₈)hydrocarbon ring,

each R¹³ is H

p′ is 2 or 3,

u is 2,

v is 1,

r′ is a number of from 1 to 25,

t′ is a number of from 1 to 25,

the product of the quantity (v+r′) multiplied times t′ is less than orequal to about 100, and

m is an integer of from 1 to 5.

In one embodiment of the organophosphorus compound according tostructure (II):

R⁶, R⁸, and each R⁷ are each H

R⁴ and R⁵ are each absent,

each R³ is independently a divalent radical according to structure(VII),

R²⁰ is hydroxyl or hydroxyalkyl,

R²² is H, alkyl, hydroxyl, or hydroxyalkyl,

R²³ and R²¹ are each independently methylene, di(methylene), ortri(methylene),

w is 1 or 2,

p″ is 2 or 3,

r″ is a number of from 1 to 25,

t″ is a number of from 1 to 25

the product of the quantity (w+r″) multiplied times t″ is less than orequal to about 100, and

m is an integer of from 1 to 5.

In one embodiment, the organophosphorus compound is according tostructure (III), each R³ is a divalent radical according to structure(V) with s=0 and t=1, R⁴ and R⁵ are each absent, and R⁶, R⁷, and R³ areeach H.

In one embodiment, the organophosphorus compound is according tostructure (IV), wherein R³ and R⁵ are each according to structure (V),with s=0 and t=1, and R⁶ and R⁸ are each H.

In one embodiment, the organophosphorus material (b)(1) comprises acondensation reaction product of two or more molecules according tostructure (I).

In one embodiment, the organophosphorus material (b)(1) comprises acondensation reaction product of two or more molecules according tostructure (I) in the form of a linear molecule, such as, for example, alinear condensation reaction product according to structure (X), formedby condensation of a molecule according to structure (II) with amolecule according to structure (IV):

wherein R⁴, R⁷, p, r are each as described above.

In one embodiment, the organophosphorus material (b)(1) comprises acondensation reaction product of two or more molecules according tostructure (I) in the form of a crosslinked network. A portion of anexemplary crosslinked condensation reaction product network isillustrated by structure (XI):

wherein

R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸, and m are each as described above, and

each R^(3′) is independently a residue of an R³ group of a compoundaccording to structure (I), as described above, wherein the R³ group isa alkyleneoxy or poly(alkyleneoxy) moiety substituted with hydroxyl-,hydroxyalkyl-, hydroxyalkyleneoxy- or hydroxypoly(alkyleneoxy)- on oneor more carbon atoms of the alkyleneoxy or poly(alkyleneoxy) moiety, and—R^(3′)—R₄— and —R^(3′)—R⁵— each represent a respective linkage formedby condensation of such an R³ group and a —R^(3′)—R⁵— or —R⁸—R⁵— groupof molecules of another molecule of a compound according to structure(I).

In one embodiment, the organophosphorus material (b)(I) comprises acondensation reaction product of two or more molecules according tostructure (I) and the condensation reaction product forms a covalentlycrosslinked organophosphorus network. Typically the solubility of thecovalently crosslinked organophosphorus network in water is less thanthat of the organophosphorus compound according to structure (I), moretypically, the covalently crosslinked organophosphorus network issubstantially insoluble in water.

As used herein, the term “salts” refers to salts prepared from bases oracids including inorganic or organic bases and inorganic or organicacids.

In one embodiment, the organophosphorus material (b)(I) is in the formof a salt that comprises an anion derived (for example, by deprotonationof a hydroxyl or a hydroxyalkyl substituent) from of an organophosphoruscompound according to structure (I) and one or more positively chargedcounterions derived from a base.

Suitable positively charged counterions include inorganic cations andorganic cations, such as for example, sodium cations, potassium cations,calcium cations, magnesium cations, copper cations, zinc cations,ammonium cations, tetraalkylammonium cations, as well as cations derivedfrom primary, secondary, and tertiary amines, and substituted amines.

In one embodiment, the cation is a monovalent cation, such as forexample, Na⁺, or K⁺.

In one embodiment, the cation is a polyvalent cation, such as, forexample, Ca⁺², Mg⁺², Zn⁺², Mn⁺², Cu⁺², Al⁺³, Fe⁺², Fe⁺³, Ti⁺⁴, Zr⁺⁴, inwhich case the organophosphorus compound may be in the form of a “saltcomplex” formed by the organophosphorus compound and the polyvalentcation. For organophosphorus compound having two or more anionic sites,e.g., deprotonated hydroxyl substituents, per molecule, theorganophosphorus compound-polyvalent cation complex can develop anionically crosslinked network structure. Typically the solubility of theionically crosslinked organophosphorus network in water is less thanthat of the organophosphorus compound according to structure (I), moretypically, the ionically crosslinked organophosphorus network issubstantially insoluble in water.

Suitable organophosphorus compounds can be made by known syntheticmethods, such as by reaction of one or more compounds, each having twoor more hydroxyl groups per molecule, with phosphoric acid,polyphosphoric acid, and or phosphoric anhydride, such as disclosed, forexample, in U.S. Pat. Nos. 5,550,274, 5,554,781, and 6,136,221.

In one embodiment, cations are immobilized on a water insolublesubstrate to form a water insoluble cationic particle and thehydrophilizing layer further comprises cationic particles. Suitablesubstrates include inorganic oxide particles, including for example,oxides of single elements, such as cerium oxide, titanium oxide,zirconium oxide, halfnium oxide, tantalum oxide, tungsten oxide, silicondioxide, and bismuth oxide, zinc oxide, indium oxide, and tin oxide, andmixtures of such oxides, as well as oxides of mixtures of such elements,such as cerium-zirconium oxides. Such particle may exhibit a meanparticle diameter (“D₅₀”) of from about 1 nanometer (“nm”) to about 50micrometers (“μm”), more typically from about 5 to about 1000 nm, evenmore typically from about 10 to about 800 nm, and still more typicallyfrom about 20 to about 500 nm, as determined by dynamic light scatteringor optical microscopy. In one embodiment, aluminum cations areimmobilized on silica particles.

Vinyl Alcohol Material

In one embodiment, the oral care product comprises a vinyl alcoholmaterial (b)(II) as a hydrophilizing material.

In one embodiment, which offers improved solubility in water andimproved processability, the vinyl alcohol material (b)(II) comprises apolymer that comprises monomeric units according to structure (I-a) (a“vinyl alcohol polymer”).

In one embodiment, the vinyl alcohol polymer and exhibits a weightaverage molecular weight of greater than or equal to about 10,000, moretypically from about 10,000 to about 100,000, even more typically fromabout 10,000 to about 30,000. In an alternative embodiment, which offersimproved durability, the vinyl alcohol polymer a weight averagemolecular weight of greater than or equal to about 100,000, moretypically form about 100,000 to about 200,000. In another embodiment,which offers a balance between processability and durability, the vinylalcohol polymer exhibits a weight average molecular weight of greaterthan or equal to about 50,000, more typically from about 50,000 to about150,000, even more typically from about 80,000 to about 120,000.

In one embodiment, the vinyl alcohol polymer is made by polymerizing avinyl ester monomer, such as for example, vinyl acetate, to form apolymer, such as a poly(vinyl acetate) homopolymer or a copolymercomprising monomeric units derived from vinyl acetate, having ahydrocarbon backbone and ester substituent groups, and then hydrolyzingat least a portion of the ester substitutent groups of the polymer toform hydroxy-substituted monomeric units according to structure (I-a).In one embodiment, which offers improved solubility in water andimproved processability, the vinyl alcohol polymer exhibits a degree ofhydrolysis of greater than or equal to about 88%, more typically fromabout 88% to about 95%. As used herein in reference to a vinyl alcoholpolymer that is made by hydrolyzing a polymer initially having ahydrocarbon backbone and ester substituent groups, the term “degree ofhydrolysis” means the relative amount, expressed as a percentage, ofvinyl ester-substituted monomeric units that were hydrolyzed to formhydroxy-substituted monomeric units. In another embodiment, which offersimproved solubility in water and improved durability, the vinyl alcoholpolymer exhibits a degree of hydrolysis of greater than or equal toabout 99%. In yet another embodiment, which offers a compromise betweensolubility in water and durability, the polymer exhibits a degree ofhydrolysis from about 92 to about 99%.

In one embodiment, the vinyl alcohol polymer has a linear polymericstructure. In an alternative embodiment, the vinyl alcohol polymer has abranched polymeric structure.

In one embodiment, the vinyl alcohol polymer is a vinyl alcoholhomopolymer that consists solely of monomeric units according tostructure (I-a).

In one embodiment, the vinyl alcohol polymer is a vinyl alcoholcopolymer that comprises monomeric units having a structure according tostructure (I-a) and further comprises comonomeric units having astructure other than structure (I-a). In one embodiment, the vinylalcohol polymer is a copolymer that comprises hydroxy-substitutedmonomeric units according to (I-a) and ester substituted monomeric unitsand is made by incomplete hydrolysis of a vinyl ester homopolymer.

In one embodiment a vinyl alcohol copolymer comprises greater than orequal to about 50 mole % (“mol %”), more typically greater or equal tothan about 80 mol %, monomeric units according to structure (I-a) andless than about 50 mol %, more typically less than about 20 mol %,comonomeric units having a structure other than structure (I-a).

As described above, vinyl alcohol polymers having monomeric unitsaccording to structure (I-a) are typically derived from polymerizationof vinyl ester monomers and subsequent hydrolysis of vinylester-substituted monomeric units of the polymer. Suitable vinyl alcoholcopolymers are typically derived by copolymerization of the vinyl estermonomer with any ethylenically unsaturated monomer that iscopolymerizable with the vinyl ester monomer, including for example,other vinyl monomers, allyl monomers, acrylic acid, methacrylic acid,acrylic ester monomers, methacrylic ester monomers, acrylamide monomers,and subsequent hydrolysis of at least a portion of the ester-substitutedmonomeric units to form hydroxy-substituted monomeric units according tostructure (I-a).

In one embodiment, the vinyl alcohol polymer comprises monomeric unitsaccording to structure (I-a) and further comprises hydrophilic monomericunits other than the monomeric according to structure (I-a). As usedherein, the term “hydrophilic monomeric units” are those whereinhomopolymers of such monomeric units are soluble in water at 25° C. at aconcentration of 1 wt % homopolymer, and include, for example, monomericunits derived from, for example, hydroxy(C₁-C₄)alkyl (meth)acrylates,(meth)acrylamide, (C₁-C₄)alkyl (meth)acrylamides,N,N-dialkyl-acrylamides, alkoxylated (meth)acrylates, poly(ethyleneglycol)-mono methacrylates and poly(ethyleneglycol)-monomethylethermethacrylates, hydroxy(C₁-C₄)acrylamides and methacrylamides,hydroxyl(C₁-C₄)alkyl vinyl ethers, N-vinylpyrrole,N-vinyl-2-pyrrolidone, 2- and 4-vinylpyridine, ethylenically unsaturatedcarboxylic acids having a total of 3 to 5 carbon atoms,amino(C₁-C₄)alkyl, mono(C₁-C₄)alkylamino(C₁-C₄)alkyl, anddi(C₁-C₄)alkylamino(C₁-C₄)alkyl (meth)acrylates, allyl alcohol,dimethylaminoethyl methacrylate, dimethylaminoethylmethacrylamide.

In one embodiment, the vinyl alcohol polymer comprises monomeric unitsaccording to structure (I-a) and further comprises hydrophobic monomericunits. As used herein, the term “hydrophobic monomeric units” are thosewherein homopolymers of such monomeric units are insoluble in water at25° C. at a concentration of 1 wt % homopolymer, and include, forexample, monomeric units derived from (C₁-C₁₈)alkyl and(C₅-C₁₈)cycloalkyl (meth)acrylates, (C₅-C₁₈)alkyl(meth)acrylamides,(meth)acrylonitrile, vinyl (C₁-C₁₈)alkanoates, (C₂-C₁₈)alkenes,(C₂-C₁₈)haloalkenes, styrene, (C¹-C₆)alkylstyrenes, (C₄-C₁₂)alkyl vinylethers, fluorinated (C₂-C₁₀)alkyl (meth)acrylates,(C₃-C₁₂)perfluoroalkylethylthiocarbonylaminoethyl (meth)acrylates,(meth)acryloxyalkylsiloxanes, N-vinylcarbazole, (C₁-C₁₂) alkyl maleic,fumaric, itaconic, and mesaconic acid esters, vinyl acetate, vinylpropionate, vinyl butyrate, vinyl valerate, chloroprene, vinyl chloride,vinylidene chloride, vinyltoluene, vinyl ethyl ether, perfluorohexylethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate,trifluoroethyl methacrylate, hexa-fluoroisopropyl methacrylate,hexafluorobutyl methacrylate, tristrimethylsilyloxysilylpropylmethacrylate, and 3-methacryloxypropylpentamethyldisiloxane.

As used herein, the term “(meth)acrylate” means acrylate, methacrylate,or acrylate and methacrylate and the term (meth)acrylamide” meansacrylamide, methacrylamide or acrylamide and methacrylamide.

In one embodiment, the polymer comprising monomeric units according tostructure (I-a) a random copolymer. In another embodiment, the copolymercomprising monomeric units according to structure (I-a) is a blockcopolymer.

Methods for making suitable vinyl alcohol polymers are known in the art.In one embodiment, a polymer comprising monomeric units according tostructure (I-a) is made by polymerizing one or more ethylenicallyunsaturated monomers, comprising at least one vinyl ester monomer, suchvinyl acetate, by known free radical polymerization processes andsubsequently hydrolyzing at least a portion of the vinyl ester monomericunits of the polymer to make a polymer having the desired degree ofhydrolysis. In another embodiment, the polymer comprising monomericunits according to structure (I-a) is a copolymer made by knowncontrolled free radical polymerization techniques, such as reversibleaddition fragmentation transfer (RAFT), macromolecular design viainterchange of xanthates (MADIX), or atom transfer reversiblepolymerization (ATRP).

In one embodiment, the vinyl alcohol polymer is made by known solutionpolymerization techniques, typically in an aliphatic alcohol reactionmedium.

In another embodiment, the vinyl alcohol polymer is made by knownemulsion polymerization techniques, in the presence of one or moresurfactants, in an aqueous reaction medium.

In one embodiment, the vinyl alcohol material comprises a microgel madeby crosslinking molecules of a vinyl alcohol polymer.

In one embodiment the vinyl alcohol material comprises a salt, such as asodium or potassium salt, of a vinyl alcohol polymer.

Compositions

The organophosphorus material described herein may also be used in avariety of oral care products. The composition according to theinvention can be provided in any form and can be used in multiple ways.Thus, it can be in the form of a paste, gel or liquid. For example, theorganophosphorus material may be used in toothpastes (as described byU.S. Pat. No. 5,939,052), and mouth detergents (as described by U.S.Pat. No. 6,767,560), and other dentifrices (as described by U.S. PatentApplication Publication No. 2004/0185207). Each of the documentsdiscussed in this paragraph are expressly incorporated by reference intheir entireties.

A toothpaste or gel in accordance with the invention will generallycomprise an organophosphorus material as described above, a surfactantagent, a compatible abrasive agent system, and a liquid in an amount toprovide the desired consistency.

In an exemplary toothpaste, the liquid may include water, humectant andbinder, generally, in an amount ranging from about 10 to about 90% byweight of the toothpaste. Water is a desirable component when atoothpaste or gel is being prepared. Water comprises up to about 50%,and preferably about 5-35% by weight of the toothpaste. However, ananhydrous toothpaste or gel can be formulated if desired.

A tooth powder in accordance with the invention may comprise a polishingagent which is compatible with the soluble monoalkyl and dialkylphosphate ester salts described herein, such as sodium bicarbonate orhydrated silica. Generally, the polishing agent will be in an amountfrom about 20 to about 95%, and preferably above 50% by weight of theformulation. An effective amount of the monoalkyl and dialkyl phosphateesters as described herein is typically from about 0.1 to about 10% andpreferably about 1% to about 5% by weight of the tooth powderformulation. Optional, but preferred, components which may be includedin the toothpowder are a flavoring agent and/or sweetening agent, ananti-calculus agent such as a water-soluble alkali metal salt of apolyphosphate, an anti-caries agent such as sodium fluoride or sodiummonofluorophosphate, buffering agents such as alkali metalorthophosphates, phosphoric acid, alkali metal glycerophosphates,tartrates, or citrates, and one or more processing aids such as a flowaid to insure product uniformity.

A mouthwash in accordance with the invention generally comprisesalcohol, water, humectant, and optionally an effective amount of themonoalkyl and dialkyl phosphate ester salts as described herein. Aneffective amount of the monoalkyl and dialkyl phosphate ester salts inthe mouthwash is typically from about 0.1% to about 10% and preferablyfrom about 1% to about 5% by weight of the mouthwash. Optional, butpreferred, components which are included in the mouthwash are aflavoring agent and/or sweetening agent, an anti-calculus agent such asa water-soluble alkali metal salt of a polyphosphate, an anti-cariesagent such as sodium fluoride or sodium monofluorophosphate, bufferingagents such as alkali metal orthophosphates, phosphoric acid, alkalimetal glycerophosphates, tartrates, or citrates.

As used herein, terms “aqueous medium” and “aqueous media” are usedherein to refer to any liquid medium of which water is a majorcomponent. Thus, the term includes water per se as well as aqueoussolutions and dispersions. For example, the aqueous medium may be aliquid bodily discharge, such as urine, menses, and saliva.

In one embodiment, the oral care composition comprises, based on 100parts by weight (“pbw”) of the composition, from about 0.1 to about 20pbw, more typically, from about 1 to about 5 pbw, organophosphorusmaterial, and from about 80 to 99 pbw, more typically, from about 90 toabout 98 pbw, carrier.

The pH of the composition or the pH of use of the composition accordingto the invention can vary, depending on the application. The pH of thecompositions is not critical and can be in the range of from about 2 toabout 12, preferably from about 4 to about 10 and most preferably fromabout 6 to about 8. The pH can be adjusted using a buffer such as citricacid.

The oral care composition of the invention can comprise, depending onits application, from 0.001 to 10% of its weight of at least one of theorganophosphorus materials (phosphate esters).

The composition can be employed in an amount such that, after optionalrinsing, the amount of phosphate esters deposited on the tooth surfaceis typically from 0.0001 to 10 mg/m², for example, 0.001 to 5 mg/m², ofsurface treated.

Unless otherwise indicated, when molar mass is referred to, thereference will be to the weight-average molar mass, expressed in g/mol.The latter can be determined by aqueous gel permeation chromatography(GPC) or by light scattering (DLS or alternatively MALLS), with anaqueous eluent or an organic eluent (for example dimethylacetamide,dimethylformamide, and the like), depending on the composition of thepolymer.

Additional Ingredients

In addition to the organophosphorus material of the present invention,oral care products, such as mouthwashes, chewing gum, soluble oral carestrips (similar to the LISTERINE® oral care strips), lozenges andtoothpastes, of the present invention contain adjunct ingredients.Additional background on such products is provided by PCT applicationserial number PCT/US98/04474, filed Mar. 6, 1998 and published as WO98/38973, as well as by U.S. Pat. No. 6,864,314, each of which isincorporated herein by reference in its entirety.

An oral hygiene composition in accordance with the invention maycomprise, without intended limitation, components customarily used inthis field, such as a polishing agent (abrasive agent), sudsing agents(surfactants), a binder, a humectant, a medicinal agent, peroxidesources, alkali metal bicarbonate salts, thickening materials, water,titanium dioxide, flavor agents, sweetening agents, xylitol, coloringagents, water and mixtures thereof. A popular, commercialanti-sensitivity agent is potassium nitrate. In preparing the presentoral care compositions, it is desirable to add one or more of theseadditional ingredients to the compositions. Such materials are wellknown in the art and are readily chosen by one skilled in the art basedon the physical and aesthetic properties desired for the compositionsbeing prepared. These additional ingredients typically comprise fromabout 40% to about 99%, preferably from about 70% to about 98%, and morepreferably from about 90% to about 95%, by weight of the dentifricecomposition.

For example, optional, but preferred, components which may be includedin oral care products in accordance with the invention are organicbinders; inorganic thickeners, such as silica; secondary surfactantsand/or sweetening agents; coloring agents and/or pigments;anti-microbial agents; and like components conventionally added totoothpastes and gels. Binders suitable for use in a composition of theinvention include hydroxyethyl cellulose, and hydroxypropyl cellulose,as well as xanthan gums, Iris moss and gum tragacanth. Binders may bepresent in the amount from 0.01 to 10%. Sweeteners suitable for use,e.g. saccharin, may be present at levels of about 0.1% to 5%.

Abrasive Polishing Materials

An abrasive polishing material may also be included in the toothpastecompositions. The abrasive polishing material contemplated for use inthe compositions of the present invention can be any material which doesnot excessively abrade dentin. Typical abrasive polishing materialsinclude silicas including gels and precipitates; aluminas; phosphatesincluding inorganic orthophosphates, pyrophosphates, metaphosphates,polyphosphates and hexametaphosphate salts; and mixtures thereof.Specific examples include dicalcium orthophosphate dihydrate, calciumpyrophosphate, tricalcium phosphate, calcium polymetaphosphate,insoluble sodium polymetaphosphate, hydrated alumina, beta calciumpyrophosphate, calcium carbonate, and resinous abrasive materials suchas particulate condensation products of urea and formaldehyde, andothers such as disclosed by Cooley et al in U.S. Pat. No. 3,070,510,issued Dec. 25, 1962, incorporated herein by reference. Mixtures ofabrasives may also be used.

Silica dental abrasives of various types are preferred because of theirunique benefits of exceptional dental cleaning and polishing performancewithout unduly abrading tooth enamel or dentine. The silica abrasivepolishing materials herein, as well as other abrasives, generally havean average particle size ranging between about 0.1 to about 30 microns,and preferably from about 5 to about 15 microns. The abrasive can beprecipitated silica or silica gels such as the silica xerogels describedin Pader et al., U.S. Pat. No. 3,538,230, issued Mar. 2, 1970, andDiGiulio, U.S. Pat. No. 3,862,307, issued Jan. 21, 1975, bothincorporated herein by reference. Preferred are the silica xerogelsmarketed under the trade name “Syloid” by the W. R. Grace & Company,Davison Chemical Division. Also preferred are the precipitated silicamaterials such as those marketed by the J. M. Tuber Corporation underthe trade name, “Zeodent”, particularly the silica carrying thedesignation “Zeodent 119”. The types of silica dental abrasives usefulin the toothpastes of the present invention are described in more detailin Wason, U.S. Pat. No. 4,340,583, issued Jul. 29, 1982, incorporatedherein by reference. Silica abrasives described in U.S. patentapplication Ser. Nos. 08/434,147 and 08/434,149, both filed May 2, 1995,are also herein incorporated by reference. The abrasive in thetoothpaste compositions described herein is generally present at a levelof from about 6% to about 70% by weight of the composition. Preferably,toothpastes contain from about 10% to about 50% of abrasive, by weightof the dentifrice composition.

Humectants

A humectant is also a desirable component in an oral care product, forexample, toothpaste or gel. The humectant generally comprises from about0% to 85%, and preferably from about 15% to 55%, by weight of the oralcare composition. Preferably for toothpaste or gel, the humectantcomprises about 5% to about 85% by weight of the formulation, andpreferably from about 10% to about 70% by weight of the formulation. Intranslucent gels, where the refractive index is an importantconsideration, it is preferred to use higher ratios of humectant towater than in opaque pastes. For a gel the ratio of humectant to watershould preferably be above about 0.5 to 1, and more preferably above 1to 1.

Humectants contemplated for use in a composition of the inventioninclude polyols, such as glycerol, sorbitol, polyethylene glycols,propylene glycol, hydrogenated partially hydrolyzed polysaccharides andthe like. Exemplary amounts are provided below with reference to varioustypes of compositions.

The humectant serves to keep toothpaste compositions from hardening uponexposure to air and certain humectants can also impart desirablesweetness of flavor to toothpaste compositions. Suitable humectants foruse in the invention include glycerin, sorbitol, polyethylene glycol,propylene glycol, and other edible polyhydric alcohols.

Anti-Caries Agent

Anti-caries agents may also be used in conjunction with the compositionin accordance with the invention. Thus, the oral care composition of thepresent invention can incorporate a soluble fluoride source capable ofproviding free fluoride ions. For example oral hygiene compositions inaccordance with the invention may include those commonly used in oralhealth care compositions, such as sodium fluoride, stannous fluoride,indium fluoride, sodium monofluorophosphate, zinc ammonium fluoride, tinammonium fluoride, calcium fluoride and cobalt ammonium fluoride and thelike. The present compositions contain a soluble fluoride ion sourcecapable of providing from about 50 ppm to about 3500 ppm, and preferablyfrom about 500 ppm to about 3000 ppm of free fluoride ions. Sodiumfluoride is the most preferred soluble fluoride ion source. Norris etal., U.S. Pat. No. 2,946,725, issued Jul. 26, 1960, and Widder et al.,U.S. Pat. No. 3,678,154 issued Jul. 18, 1972, disclose such fluoride ionsources as well as others. Both patents are incorporated herein byreference in their entirety.

Dyes/Colorants

Dyes/colorants suitable for oral health care compositions, i.e. FD & CBlue #1, FD & C Yellow #10, FD & C Red #40, etc., may be included aswell. Various other optional ingredients may also be included in thecompositions of the invention such as preservatives; vitamins, forexample, vitamins C and E; and other anti-plaque agents, for example,stannous salts, copper salts, strontium salts and magnesium salts.Compositions may also include anti-calculus agents such as awater-soluble alkali metal salt of a polyphosphate, buffering agentssuch as alkali metal orthophosphates, phosphoric acid, alkali metalglycerophosphates, tartrates, or citrates, other anti-caries agents, forexample, calcium glycerophosphate, sodium trimetaphosphate;anti-staining compounds, for example silicone polymers; plant extracts;and mixtures thereof. Additionally, polymers, particularly anionicpolymers, such as polycarboxylates or polysulfonates, or polymerscontaining both a carboxylate and a sulfonate moiety, or phosphonatepolymers may be used.

Buffering Agents

The present compositions each may contain a buffering agent. Bufferingagents, as used herein, refer to agents that can be used to adjust thepH of the compositions to a range of about pH 6.5 to about pH 10. Theseagents include alkali metal hydroxides, carbonates, sesquicarbonates,borates, silicates, phosphates, imidazole, and mixtures thereof.Specific buffering agents include monosodium phosphate, trisodiumphosphate, sodium hydroxide, potassium hydroxide, alkali metal carbonatesalts, sodium carbonate, imidazole, pyrophosphate salts, citric acid,and sodium citrate. Buffering agents are used at a level of from about0.1% to about 30%, preferably from about 1% to about 10%, and morepreferably from about 1.5% to about 3%, by weight of the presentcomposition.

Inorganic pyrophosphate salts are also suitable buffering agents. Thepyrophosphate salts include the dialkali metal pyrophosphate salts,tetra alkali metal pyrophosphate salts, and mixtures thereof. Disodiumdihydrogen pyrophosphate (Na₂H₂P₂O₇), tetrasodium pyrophosphate(Na₄P₂O₇), and tetrapotassium pyrophosphate (K₄P₂O₇) in their unhydratedas well as hydrated forms are the preferred species. In compositions ofthe present invention, the pyrophosphate salt may be present in one ofthree ways: predominately dissolved, predominately undissolved, or amixture of dissolved and undissolved pyrophosphate.

Compositions comprising predominately dissolved pyrophosphate refer tocompositions where at least one pyrophosphate ion source is in an amountsufficient to provide at least about 1.0% free pyrophosphate ions. Theamount of free pyrophosphate ions may be from about 1% to about 15%,preferably from about 1.5% to about 10%, and most preferably from about2% to about 6%, by weight of the composition. Free pyrophosphate ionsmay be present in a variety of protonated states depending on the pH ofthe composition.

Compositions comprising predominately undissolved inorganicpyrophosphate refer to compositions containing no more than about 20% ofthe total pyrophosphate salt dissolved in the composition, preferablyless than about 10% of the total pyrophosphate dissolved in thecomposition. Tetrasodium pyrophosphate salt is the preferredpyrophosphate salt in these compositions. Tetrasodium pyrophosphate maybe the anhydrous salt form or the decahydrate form, or any other speciesstable in solid form in the dentifrice compositions. The salt is in itssolid particle form, which may be its crystalline and/or amorphousstate, with the particle size of the salt preferably being small enoughto be aesthetically acceptable and readily soluble during use. Theamount of pyrophosphate salt useful in making these compositions is anytartar control effective amount, and is generally from about 1.5% toabout 15%, preferably from about 2% to about 10%, and most preferablyfrom about 2.5% to about 8%, by weight of the composition. Some or allof the tetrasodium pyrophosphate may be undissolved in the product andpresent as tetrasodium pyrophosphate particles. Pyrophosphate ions indifferent protonated states (e.g., HP₂O₇ ⁻³) may also exist dependingupon the pH of the composition and if part of the tetrasodiumpyrophosphate is dissolved.

Compositions may also comprise a mixture of dissolved and undissolvedpyrophosphate salts. Any of the above mentioned pyrophosphate salts maybe used.

The pyrophosphate salts are described in more detail in Kirk & Othmer,Encyclopedia of Chemical Technology, Third Edition, Volume 17,Wiley-Interscience Publishers (1982), incorporated herein by referencein its entirety, including all references incorporated into Kirk &Othmer.

Optional agents to be used in place of or in combination with thepyrophosphate salt include such materials known to be effective inreducing calcium phosphate mineral deposition related to calculusformation. Agents included are synthetic anionic polymers [includingpolyacrylates and copolymers of maleic anhydride or acid and methylvinyl ether (e.g., Gantrez), as described, for example, U.S. Pat. No.4,627,977, to Gaffar et al., the disclosure of which is incorporatedherein by reference in its entirety; as well as, e.g., polyaminopropoane sulfonic acid (AMPS), zinc citrate trihydrate, diphosphonates(e.g., EHDP; AHP), polypeptides (such as polyaspartic and polyglutamicacids), and mixtures thereof.

Thickening Agents

The present invention compositions in the form of toothpastes typicallycontain some thickening material or binders to provide a desirableconsistency. Preferred thickening agents are carboxyvinyl polymers,carrageenan, hydroxyethyl cellulose, and water soluble salts ofcellulose ethers such as sodium carboxymethylcellulose and sodiumhydroxyethyl cellulose. Natural gums such as gum karaya, xanthan gum,gum arabic, and gum tragacanth can also be used. Colloidal magnesiumaluminum silicate or finely divided silica can be used as part of thethickening agent to further improve texture. Thickening agents can beused in an amount from about 0.1% to about 15%, by weight of thedentifrice composition.

Water

Water employed in the preparation of commercially suitable oralcompositions should preferably be of low ion content and free of organicimpurities. Water can generally comprise from about 5% to about 70%, andpreferably from about 10% to about 50%, by weight of the compositionherein. The amounts of water include the free water which is added plusthat which is introduced with other materials, such as with sorbitol,silica, surfactant solutions, and/or color solutions.

Peroxide

The present invention may include a peroxide source in the composition.The peroxide source can be selected from the group consisting ofhydrogen peroxide, calcium peroxide, urea peroxide, and mixturesthereof. The preferred peroxide source is calcium peroxide. Thefollowing amounts represent the amount of peroxide raw material,although the peroxide source may contain ingredients other than theperoxide raw material. The present composition may contain from about0.01% to about 10%, preferably from about 0.1% to about 5%, morepreferably from about 0.2% to about 3%, and most preferably from about0.3% to about 0.8% of a peroxide source, by weight of the dentifricecomposition.

Alkali Metal Bicarbonate Salt

The present invention may also include an alkali metal bicarbonate salt.Alkali metal bicarbonate salts are soluble in water and unlessstabilized, tend to release carbon dioxide in an aqueous system. Sodiumbicarbonate, also known as baking soda, is the preferred alkali metalbicarbonate salt. The alkali metal bicarbonate salt also functions as abuffering agent. The present composition may contain from about 0.5% toabout 50%, preferably from about 0.5% to about 30%, more preferably fromabout 2% to about 20%, and most preferably from about 5% to about 18% ofan alkali metal bicarbonate salt, by weight of the dentifricecomposition.

Sudsing Agents

The present compositions may also comprise surfactants, also commonlyreferred to as sudsing agents. Suitable surfactants are those which arereasonably stable and foam throughout a wide pH range. The surfactantmay be anionic, nonionic, amphoteric, zwitterionic, cationic, ormixtures thereof. Anionic surfactants useful herein include thewater-soluble salts of alkyl sulfates having from 8 to 20 carbon atomsin the alkyl radical (e.g., sodium alkyl sulfate) and the water-solublesalts of sulfonated monoglycerides of fatty acids having from 8 to 20carbon atoms. Sodium lauryl sulfate and sodium coconut monoglyceridesulfonates are examples of anionic surfactants of this type. Othersuitable anionic surfactants are sarcosinates, such as sodium lauroylsarcosinate, taurates, sodium lauryl sulfoacetate, sodium lauroylisethionate, sodium laureth carboxylate, and sodium dodecylbenzenesulfonate. Mixtures of anionic surfactants can also be employed.Many suitable anionic surfactants are disclosed by Agricola et al., U.S.Pat. No. 3,959,458, issued May 25, 1976, incorporated herein in itsentirety by reference. Nonionic surfactants which can be used in thecompositions of the present invention can be broadly defined ascompounds produced by the condensation of alkylene oxide groups(hydrophilic in nature) with an organic hydrophobic compound which maybe aliphatic or alkyl-aromatic in nature. Examples of suitable nonionicsurfactants include poloxamers (sold under trade name Pluronic),polyoxyethylene, polyoxyethylene sorbitan esters (sold under trade nameTWEENS), fatty alcohol ethoxylates, polyethylene oxide condensates ofalkyl phenols, products derived from the condensation of ethylene oxidewith the reaction product of propylene oxide and ethylene diamine,ethylene oxide condensates of aliphatic alcohols, long chain tertiaryamine oxides, long chain tertiary phosphine oxides, long chain dialkylsulfoxides, and mixtures of such materials. The amphoteric surfactantsuseful in the present invention can be broadly described as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be a straight chain or branched and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic water-solubilizing group, e.g., carboxylate,sulfonate, sulfate, phosphate, or phosphonate. Other suitable amphotericsurfactants are betaines, specifically cocamidopropyl betaine. Mixturesof amphoteric surfactants can also be employed. Many of these suitablenonionic and amphoteric surfactants are disclosed by Gieske et al., U.S.Pat. No. 4,051,234, issued Sep. 27, 1977, incorporated herein byreference in its entirety. The present composition typically comprisesone or more surfactants each at a level of from about 0.25% to about12%, preferably from about 0.5% to about 8%, and most preferably fromabout 1% to about 6%, by weight of the composition.

Colorants

Titanium dioxide may also be added to the present composition. Titaniumdioxide is a white powder which adds opacity to the compositions.Titanium dioxide generally comprises from about 0.25% to about 5%, byweight of the composition.

Other coloring agents may also be added to the present composition. Thecoloring agent may be in the form of an aqueous solution, preferably 1%coloring agent in a solution of water. Color solutions generallycomprise from about 0.01% to about 5%, by weight of the composition.

Dyes/colorants suitable for oral health care compositions, i.e. FD & CBlue #1, FD & C Yellow #10, FD & C Red #40, etc., may be included aswell. Various other optional ingredients may also be included in thecompositions of the invention such as preservatives; vitamins, forexample, vitamins C and E; and other anti-plaque agents, for example,stannous salts, copper salts, strontium salts and magnesium salts.Compositions may also include anti-calculus agents such as awater-soluble alkali metal salt of a polyphosphate, buffering agentssuch as alkali metal orthophosphates, phosphoric acid, alkali metalglycerophosphates, tartrates, or citrates, other anti-caries agents, forexample, calcium glycerophosphate, sodium trimetaphosphate;anti-staining compounds, for example silicone polymers; plant extracts;and mixtures thereof. Additionally, polymers, particularly anionicpolymers, such as polycarboxylates or polysulfonates, or polymerscontaining both a carboxylate and a sulfonate moiety, or phosphonatepolymers may be used.

Flavor and Sweetening Agents

A flavor system can also be added to the compositions. Suitableflavoring components include oil of wintergreen, oil of peppermint, oilof spearmint, clove bud oil, menthol, anethole, methyl salicylate,eucalyptol, cassia, 1-menthyl acetate, sage, eugenol, parsley oil,oxanone, alpha-irisone, marjoram, lemon, orange, propenyl guaethol,cinnamon, vanillin, ethyl vanillin, heliotropine, 4-cis-heptenal,diacetyl, methyl-para-tert-butyl phenyl acetate, and mixtures thereof.Coolants may also be part of the flavor system. Preferred coolants inthe present compositions are the paramenthan carboxyamide agents such asN-ethyl-p-menthan-3-carboxamide (known commercially as “WS-3”) andmixtures thereof. A flavor system is generally used in the compositionsat levels of from about 0.001% to about 5%, by weight of thecomposition.

The present invention may also include xylitol. Xylitol is a sugaralcohol that is used as a sweetener and humectant. Xylitol may provide atherapeutic effect, such as an antibacterial or anticarries effect. Thepresent compositions typically comprise xylitol at a level from about0.01% to about 25%, preferably from about 3% to about 15%, morepreferably from about 5% to about 12%, and most preferably from about 9%to about 11%, by weight of the total composition. Alternatively, ifxylitol is used as a sweetener, it may be present at a lower level, suchas from about 0.005% to about 5%, by weight of the dentifricecomposition.

Other sweetening agents can be added to the compositions. These includesaccharin, dextrose, sucrose, lactose, maltose, levulose, aspartame,sodium cyclamate, D-tryptophan, dihydrochalcones, acesulfame, andmixtures thereof. Various coloring agents may also be incorporated inthe present invention. Sweetening agents and coloring agents aregenerally used in toothpastes at levels of from about 0.005% to about5%, by weight of the composition.

Antibacterial and Antimicrobial Agents

The present invention may also include other agents, such asantibacterial agents and antimicrobial agents. Suitable antibacterialagents include phenolics and salicylamides.

Also, included among such agents are water insoluble non-cationicantimicrobial agents such as halogenated diphenyl ethers, phenoliccompounds including phenol and its homologs, mono and poly-alkyl andaromatic halophenols, resorcinol and its derivatives, bisphenoliccompounds and halogenated salicylanilides, benzoic esters, andhalogenated carbanilides. The water soluble antimicrobials includequaternary ammonium salts and bis-biquanide salts, among others.Triclosan monophosphate is an additional water soluble antimicrobialagent. The quaternary ammonium agents include those in which one or twoof the substitutes on the quaternary nitrogen has a carbon chain length(typically alkyl group) from about 8 to about 20, typically from about10 to about 18 carbon atoms while the remaining substitutes (typicallyalkyl or benzyl group) have a lower number of carbon atoms, such as fromabout 1 to about 7 carbon atoms, typically methyl or ethyl groups.Dodecyl trimethyl ammonium bromide, tetradecylpyridinium chloride,domiphen bromide, N-tetradecyl-4-ethyl pyridinium chloride, dodecyldimethyl (2-phenoxyethyl) ammonium bromide, benzyl dimethylstearylammonium chloride, cetyl pyridinium chloride, quaternized5-amino-1,3-bis(2-ethyl-hexyl)-5-methyl hexa hydropyrimidine,benzalkonium chloride, benzethonium chloride and methyl benzethoniumchloride are exemplary of typical quaternary ammonium antibacterialagents. Other compounds are bis[4-(R-amino)-1-pyridinium] alkanes asdisclosed in U.S. Pat. No. 4,206,215, issued Jun. 3, 1980, to Bailey,incorporated herein by reference. Stannous salts such as stannouspyrophosphate and stannous gluconate and other antimicrobials such ascopper bisglycinate, copper glysinate, zinc citrate, and zinc lactatemay also be included.

Also useful are enzymes, including endoglycosidase, papain, dextranase,mutanase, and mixtures thereof. Such agents are disclosed in U.S. Pat.No. 2,946,725, Jul. 26, 1960, to Norris et al. and in U.S. Pat. No.4,051,234, Sep. 27, 1977 to Gieske et al., incorporated herein byreference. Specific antimicrobial agents include chlorhexidine,triclosan, triclosan monophosphate, and flavor oils such as thymol.Triclosan and other agents of this type are disclosed in Parran, Jr. etal., U.S. Pat. No. 5,015,466, issued May 14, 1991, and U.S. Pat. No.4,894,220, Jan. 16, 1990 to Nabi et al., incorporated herein byreference. The water insoluble antimicrobial agents, water solubleagents, and enzymes may be present in the composition. The quaternaryammonium agents, stannous salts, and substituted guanidines arepreferably present in the second dentifrice composition. These agentsmay be present at levels of from about 0.01% to about 1.5%, by weight ofthe dentifrice composition.

To further illustrate the invention and the advantages thereof, thefollowing non-limiting examples are given.

Example 1 Egg Shell Tests

In this example egg-shell (as a substitute for teeth) was stained withgreen/black tea stain.

FIG. 1 shows a photograph of egg-shell brushed with commercialtoothpaste, then stained with green (left) and black (right) tea, andthen brushed again with commercial tooth-paste. This resulted in noremoval of tea stain.

In another experiment PEG400 phosphate ester (a polyethylene glycolphosphate ester) was mixed directly into the toothpaste withoutneutralization. Egg-shell was brushed with commercial toothpaste plus20% PEG400 phosphate ester, then stained with green and black tea, andthen brushed again with commercial tooth-paste plus 20% PEG400 phosphateester. FIG. 2 shows a photograph of the egg-shell brushed with thecommercial toothpaste plus 20% PEG400 phosphate ester, then stained withgreen (left) and black (right) tea, and then brushed again withcommercial tooth-paste plus 20% PEG400 phosphate ester. This resulted ingood removal of tea stain.

In another experiment 20% sodium dodecyl sulphate (SDS) was mixed intothe commercial toothpaste. The 20% SDS was used as a 100% powder. FIG. 3shows a photograph of egg-shell brushed with the commercial toothpasteplus 20% SDS, then stained with green (left) and black (right) tea, andthen brushed with commercial toothpaste plus 20% SDS. This resulted inno/slight removal of tea stain.

In another experiment PEG1000 phosphate ester (a polyethylene glycolphosphate ester) was mixed directly into the toothpaste withoutneutralization. FIG. 4 shows a photograph of egg-shell brushed with thecommercial toothpaste plus 20% PEG1000 phosphate ester, then stainedwith green (left) and black (right) tea, and then brushed again withcommercial toothpaste plus 20% PEG1000 phosphate ester. This resulted ingood removal of tea stain.

In a separate test it was noted that treatment of egg-shell with SDS orPEG phosphate ester, then staining and then simple rinsing does notimprove removal of stain compared to untreated egg-shell. This impliesimproved cleaning is not due to creation of anti-soiling layer, but dueto better cleaning capability.

Example 2

FIG. 5 shows a droplet of hexadecane under pure deionized water on CaCO₃crystal (as an additional substitute for teeth). FIG. 7 is FIG. 5labeled to show the contact angle. FIG. 7 shows the contact angle was60°-80°.

FIG. 6 shows a droplet of hexadecane under a solution containing 1 wt %PEG1000 phosphate ester at a pH of 10 on a CaCO₃ crystal. This shows thepresence of PEG1000 phosphate ester, eases the contact angle ofhexadecane on CaCO₃. The pretreatment of calcium carbonate crystal wasdone by immersing the crystal in an aqueous solution of e.g. PEG1000phosphate ester (e.g. 1 wt %, pH 9-10). A successful adsorption onto thecrystal and a respective change of the surface properties is shown bymeasuring the contact angle of hexadecane. FIG. 8 is FIG. 6 labeled toshow the contact angle. FIG. 8 shows the contact angle was >130°.

Comparison of FIGS. 7 and 8 shows the presence of PEG1000 phosphateester onto the CaCO₃ crystal increases the contact angle of hexadecaneon CaCO₃ from <80° to >130°.

Thus, a low contact angle is observed for the crystal in pure water(i.e. good adsorption of the oil onto the crystal, which is undesirable)and a high contact angle is observed for the crystal in a solution ofwater and PEG 1000 phosphate ester (i.e. poor adsorption of the oil ontothe crystal, which is desirable).

It is apparent that embodiments other than those expressly describedabove come within the spirit and scope of the present claims. Thus, thepresent invention is not defined by the above description, but rather isdefined by the claims appended hereto.

1. An oral care composition, comprising: (a) from about 10% to about 99%of at least one ingredient selected from the group consisting of anabrasive polishing agent, sudsing agents, surfactants, a binder, ahumectant, a medicinal agent, peroxide sources, alkali metal bicarbonatesalts, thickening materials, titanium dioxide, flavor agents, sweeteningagents, xylitol, coloring agents, water and mixtures thereof, and (b) aneffective amount of an anti-stain agent comprising: (b)(I)(1)organophosphorus compounds according to structure (I):

wherein: each R¹ is and each R² is independently absent or O, providedthat at least one of R¹ and R² is O, each R³ is independentlyalkyleneoxy, poly(alkyleneoxy), which may optionally, be substituted onone or more carbon atom of such alkyleneoxy, or poly(alkyleneoxy) groupby hydroxyl, alkyl, hydroxyalkyl, alkoxy, alkenyl, aryl, or aryloxy, R⁵is and each R⁴ is independently absent or alkyleneoxy,poly(alkyleneoxy), which may optionally, be substituted on one or morecarbon atom of such alkyleneoxy, or poly(alkyleneoxy) group by hydroxyl,alkyl, hydroxyalkyl, alkoxy, alkenyl, aryl, or aryloxy, R⁶ and R⁸ areeach and each R⁷ is independently H or —POR⁹R¹⁰, R⁹ and R¹⁰ are eachindependently hydroxyl, and m is an integer of from 1 to 5, (b)(I)(2)salts of organophosphorus compounds according to structure (I),(b)(I)(3) condensation reaction products of two or more molecules of oneor more organophosphorus compounds according to structure (I), and(b)(I)(4) mixtures comprising two or more of the compounds, salts,and/or reaction products of (b)(I)(1), (b)(I)(2), and (b)(I)(3).
 2. Theoral care composition of claim 1, further comprising sodium carbonate asa buffering agent.
 3. The oral care composition of claim 2, wherein saidabrasive polishing agent is selected from the group consisting ofsilicas, aluminas, phosphates, orthophosphates, polymetaphosphates, betacalcium pyrophosphate, calcium carbonate, and mixtures thereof andwater.
 4. The oral care composition of claim 1, comprising about 0.01%to about 10% of a peroxide source, and at least one ingredient selectedfrom the group consisting of an abrasive polishing agent, sudsingagents, surfactants, a binder, a humectant, a medicinal agent, alkalimetal bicarbonate salts, thickening materials, titanium dioxide, flavoragents, sweetening agents, xylitol, coloring agents, water and mixturesthereof.
 5. The oral care composition of claim 4, wherein the at leastone ingredient is selected from the group consisting of surfactants,thickening materials, humectants, water, titanium dioxide, flavorsystems, sweetening agents, xylitol, coloring agents, and mixturesthereof.
 6. The oral care composition of claim 1, wherein theorganophosphorus material is present in a liquid carrier.
 7. The oralcare composition of claim 1, wherein the composition is a tooth cleaningproduct, comprising the organophosphorus material, a surfactant agent,an abrasive agent and optionally a liquid.
 8. The oral care compositionof claim 7, wherein the abrasive agent is an abrasive system comprisingone or more of hydrated silica, colloidal silica, fumed silica,insoluble sodium metaphosphate, insoluble sodium aluminosilicates,sodium bicarbonate or mixtures thereof.
 9. The oral care composition ofclaim 8, wherein the abrasive system is in amount of from about 5% toabout 70% by weight of the tooth cleaning product.
 10. The oral carecomposition of claim 7, wherein the tooth cleaning product is atoothpaste or a tooth cleaning gel.
 11. The oral care composition ofclaim 7, wherein the liquid comprises one or more of water, humectant,binder, or a mixture thereof.
 12. The oral care composition of claim 11,wherein the liquid is in an amount of from about 10% to about 90% byweight of the tooth cleaning product.
 13. The oral care composition ofclaim 11, wherein the humectant is in an amount of from about 5% toabout 85% of the tooth cleaning product.
 14. The oral care compositionof claim 7, wherein the tooth cleaning product is a translucent gelhaving a humectant to water ratio of at least about 0.5 to
 1. 15. Theoral care composition of claim 1, wherein the composition is a toothpowder comprising: an effective amount of the organophosphorus material;and from about 20% to about 95% by weight of a polishing agent.
 16. Theoral care composition of claim 15, wherein the effective amount oforganophosphorus material is from about 0.1% to about 10% by weight ofthe tooth powder.
 17. The oral care composition of claim 15, wherein theeffective amount of organophosphorus material is from about 1% to about5% by weight of said tooth powder.
 18. The oral care composition ofclaim 15, comprising from over 50% by weight polishing agent.
 19. Theoral care composition of claim 15, further comprising one or more of, ananti-calculus agent, an anti-caries agent, buffering agents, orprocessing aids.
 20. The oral care composition of claim 1, wherein thecomposition is a mouthwash comprising: an effective amount of theorganophosphorus material to remove stains from teeth; alcohol;humectant; and water.
 21. The oral care composition of claim 20, whereinthe effective amount of the organophosphorus material is from about 0.1%to about 10% by weight of the mouthwash.
 22. The oral care compositionof claim 20, wherein the effective amount of the organophosphorusmaterial is from about 1% to about 5% by weight of the mouthwash. 23.The oral care composition of claim 20, further comprising one or moreof, sweetening agent, an anti-calculus agent, an anti-caries agent,buffering agents, or processing aids.
 24. A toothpaste comprising theoral care composition of claim
 1. 25. A chewing gum comprising the oralcare composition of claim
 1. 26. A mouthwash comprising the oral carecomposition of claim
 1. 27. An oral care strip comprising the oral carecomposition of claim
 1. 28. A lozenge comprising the oral carecomposition of claim
 1. 29. A method for cleaning teeth comprisingapplying an effective amount of the composition of claim 1 to teeth inneed of cleaning.
 30. The oral care composition of claim 1, wherein eachR¹ and each R² is O, and the organophosphorus compound is selected from:(II)(1) an organophosphate ester according to structure (II):


31. The composition of claim 1, wherein each R¹ is absent, each R² is O,and the organophosphorus compound is selected from: (III)(1) anorganophosphonate ester according to structure (III):


32. The composition of claim 1, wherein each R¹ is O, each R² is absent,and the organophosphorus compound is selected from: (IV)(1) anorganophosphonate ester according to structure (IV):


33. The composition of claim 1, each R³ is a divalent radical accordingto structure (V), (VI), (VII), or (VIII):

wherein: each R¹² and each R¹³ is independently H, hydroxyl, alkyl,hydroxyalkyl, alkoxy, alkenyl, aryl, aryloxy, or two R¹² groups that areattached to the adjacent carbon atoms may be fused to form, togetherwith the carbon atoms to which they are attached, a (C₆-C₈)hydrocarbonring, R²⁰ is H, H hydroxyl, alkyl, hydroxyalkyl, alkoxy, alkenyl, aryl,or aryloxy R²² is hydroxyl or hydroxyalkyl, provided that R²⁰ and R²²are not each hydroxyl, R²³ and R²¹ are each independently methylene orpoly(methylene), p, p′, p″, q, and x are each independently integers offrom 2 to 5, each r, s, r′, r″, and y is independently a number of from0 to 25, provided that at least one of r and s is not 0, u is an integerof from 2 to 10, v and w are each numbers of from 1 to 25, and t, t′,and t″ are each numbers of from 1 to 25, provided that the product ofthe quantity (r+s) multiplied times t is less than or equal to about100, the product of the quantity (v+r′) multiplied times t′ is less thanor equal to about 100, and the product of the quantity (w+r″) multipliedtime t″ is less than or equal to about
 100. 34. The composition of claim1, wherein the organophosphorus material is selected from: (X)(1)organophosphorus compounds according to structure (IX):

wherein: p is 2, 3, or 4, more typically 2 or 3, r is a number of from 4to about 50, (IX)(2) salts organophosphorus compounds according tostructure (IX), and (IX)(3) mixtures comprising two or more of thecompounds and/or salts of (IX)(1) and (IX)(2).
 35. The composition ofclaim 30, wherein the organophosphorus compound according to structure(II): R⁶, R⁸, and each R⁷ are each H, R⁴ and R⁵ are each absent, each R³is independently a divalent radical according to structure (VI),

the R¹² groups are fused to form, including the carbon atoms to whichthey are attached, a (C₆-C₈)hydrocarbon ring, each R¹³ is H p′ is 2 or3, u is 2, v is 1, r′ is a number of from 1 to 25, t′ is a number offrom 1 to 25, the product of the quantity (v+r′) multiplied times t′ isless than or equal to about 100, and m is an integer of from 1 to
 5. 36.The composition according to claim 30, wherein the organophosphoruscompound according to structure (II): R⁶, R⁸, and each R⁷ are each H, R⁴and R⁵ are each absent, each R³ is independently a divalent radicalaccording to structure (VII),

R²⁰ is hydroxyl or hydroxyalkyl, R²² is H, alkyl, hydroxyl, orhydroxyalkyl, provided that R²⁰ and R²² are not each hydroxyl, R²³ andR²¹ are each independently methylene, di(methylene), or tri(methylene),w is 1 or 2, p″ is 2 or 3, r″ is a number of from 1 to 25, t″ is anumber of from 1 to 25 the product of the quantity (w+r″) multipliedtimes t″ is less than or equal to about 100, and m is an integer of from1 to
 5. 37. The composition according to claim 31, wherein theorganophosphorus compound is according to structure (III), each R³ is adivalent radical according to structure (V),

p and q are each independently integers of from 2 to 5, s=0 and t=1, R⁴and R⁵ are each absent, and R⁶, R⁷, and R⁸ are each H, each r is anumber of from 1 to
 25. 38. The composition according to claim 32,wherein the organophosphorus compound is according to structure (IV),wherein R3 and R5 are each according to structure (V),

p and q are each independently integers of from 2 to 5, s=0 and t=1, andR⁶, R⁷, and R⁸ are each H, each r is a number of from 1 to
 25. 39. Theoral care composition of claim 1, wherein at least one of R⁶, R⁸ and R⁷is —POR⁹R¹⁰.